Photographic color material and process utilizing 5-pyrazolone color couplers



y 1963 M. J. MONBALIU ET AL 3,393,071

PHOTOGRAPHIC COLOR MATERIAL AND PROCESS UTILIZING -PYRAZOLONE COLOR COUPLERS Filed Oct. 8, 1964 2 Sheets-Sheet 1 ATTORNEYS y 1 1968 M. J. MONBALlU ET AL 3,393,071

PHOTOGRAPHIC COLOR MATERIAL AND PROCESS UTILIZING S-PYRAZOLONB COLOR COUPLERS Filed Oct. 8, 1964 2 Sheets-Sheet I I I I 6 600 W4 ralrgfln 49274112704;

\Q N a x g Qfi INVENTOR-S Wig/ W A. u: flazzalz'w 571 5 a a I e ATTORNEY6 United States Patent ABSTRACT or THE DISCLOSURE S-pyrazolone color couplers having a urea linkage in combination with an alkyl group at the 3 position are described. The color couplers of the invention possess favorable spectral properties for use in positive and reversal color materials.

This invention relates to the manufacture of photographic color images.

The present application is a-continuation-in-part of our application Ser. No. 314,807, filed Oct. 8, 1963, now abandoned. I

It is known that for the manufacture of a photographic color image in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the" presence of'a color coupler which by reaction with the oxidized developing substances forms a dye on the areas corresponding with the silver image.

'In the subtractive three-color photography mostly a light-sensitive photographic color material is used comprising a red-sensitized, a green-sensitized and a bluesensitive silver halide emulsion layer wherein on development by means of suitable color couplers, a cyan, a magenta anda'yello'w dye image are formed respectively. As known, distinction should be made between color couplers for'negative andpositive materials e.g. with respect to theabsorption spectrum of the dyes to be formed.

It is an object of the present invention to provide a method for the manufacture of photographic color images by means of color couplers which on color development with an aromatic primary amine as adeveloping substance form a magenta dye possessing favorable spectral properties for'use in' positive and reversal color material.

- "Another object of this invention is to provide photographic processing baths and photographic materials containingfifromS jto' carbon atoms, e.g. an n-octadecyl ra cah' nd' R represents anguns ubstitu'tedarylgroup, e.g. a phenyl .group' or 'a substituted jaryl group, eg an alkyl-substitute'd phenyl Tg'roup, 1am; alkoxy-substit-uted phenyl 1 gr'onp ,a phenyloxy-subsjtituted,phenyl group, a halogensubstituted phenyl group, an alkylsulfonyl-substituted phenyl group, an arylsul' fony bstituted phenyl group,

a sulfamyl group and an N-substit uted sulfamylphenyl p- These color couplers can be prepared according to a method described in the U.S. patent application Ser. No. 314,594

When the said color couplers do not contain a radical rendering the molecule fast to diffusion; they can be used in the developing solution. Preferably, however, they are incorporated in a non-migratory form into a light-sensitive silver halide emulsion layer or a non-light-sensitive waterpermeable colloid layer, which is in direct contact with'a light-sensitive layer or which is separated from it by a water-permeable layer. The color couplers used according to this invention are preferably rendered fast to diffusion by the introductionintheir molecule of an acyclic aliphatic radical containing of from 5 to 20 carbon atoms in straight line.

New non-diffusing color couplers, which according to the present invention are preferably incorporated into the photographic material, have the following structure:

These color couplers may alsofbe incorporated in a silver halide emulsion layer according to themethods of Mannes and Godowsky, U.S. patent specification 2,304,940 and of Jelley and Vittum, US. patent specification 2,322 027. In the process of the latter patent specification the coupler is first dissolved in a water-insoluble high-boiling organic crystalloidal material such as,1,2 -dimethoxybenzene or dimethyl phthalate, and the solution is then dispersed in the silver halide emulsion.

According to a preferred embodiment for. the manufacture of a light-sensitive color material according to the present invention, the 2 -pyrazolin-5-one color couplers used in the present invention,.which are rendered fast. to diffusion by the introduction of a long aliphatic chain in their molecule, are dissolved in a Water-miscible solvent such as ethanol and homogeneously mixedwith the lightsensitive silver halide emulsion during the preparation of the latter. The silver halide emulsion normally contains the usual colloids such as gelatin, poly(vinyl alcohol), collodion or other natural or synthetic colloids suitabl therefor. V

The magenta-forming color coupler usually is added to the green-sensitized silver halide emulsion. According to a preferred embodiment this silver halide emulsion is applied as a second color coupler containing layer of a photographic multilayer color material. Such multilayer material usually comprises the f-ollowinglayers in the indicated sequence: a support, a red-sensitized silver halide emulsion layer containing a cyan-forming color coupler, a green-sensitized silver halide emulsion layer containing a magenta-forming color coupler, a yellow filter layer mostly consisting of gelatin containing dispersed colloidal silver, and a blue-sensitive silver halide emuslion layer containing a yellow-forming color coupler.

In the development of exposed photographic silver halide emulsion layers, using the-couplers described above, any color-forming developer containing a primary amino group may be used. These include'developers having two primary amino groupsas well as those having one of the amino groups substituted.ohhaving sub's'tituents in the ring such as alkylphenylen'ei-diamines, These .compounds are usually used in the salt form such a s the hydrochloride or the sulfate, which are more. stable than the amines themselves. All of these compoundsh ve an unsubstituted amino group, which enables the oxidation p'roducts of the developer to couple with the color-forming compounds to form a dye.

Suitable developing substances are aromatic primary amino compounds such as p-phenylenediamine and derivatives thereof such as N,N-diethyl-N -sulfomethyl-p-phenylenediamine and N,N-diethyl- N-carboxymethyl-p-phenylenediamine. f

,One of v the advantages. of the couplers usedaccording to our invention is l thatjthe' dyes formed by coupling with an oxidized developing compound e.g'. N,N-diethyl-pphenylenediamine have an absorption curve with a'very steep slope on the side of the long wave-lengths and with a very high transmission in the blue region of the visible spectrum.

The absorption curves represented in the accompanying drawings demonstrate clearly the favorable low transmission in theblue and the steep slope of the absorption curves of dyes obtained by means of color couplers used according to the present invention in respect ofthe transmission and the slope of'the absorption curves of dyes obtained with color couplers of a type described in 'U.S. patentspecification 2 ,369,489.

FIGURE 1 represents the absorption curves A and B of the dyestuffs that are formed by development with N,N-diethyl-p-phenylenediamine of the color couplers having respectively the followingstructural formulas:

The following examples illustrate the invention.

"Example! To /2. kg. of a green-sensitive silver halide'emulsion containing 0.0950 mol of. silver chloride are added'lO g. of the color coupler having the structural Formula 4 dis.- solved ina mixture of 40 ml. of l N sodium hydroxide, ml. of isopropanol and 32 ml. of distilled w'aterQAfter addition of the usual additives such as hardeners, wetting agents, stabilizers and the necessary amount of distilled water-to obtain-1 kg. of emulsion,fit'he latter is coated onto a cellulose triacetate support and dried.

After exposure with green light through a grey wedge, the photographic material is developed for 7.5 'min'fat 20C. in a color-developing bath of the following composition:

N,N-diethyl-p-phenylenedia-mine hydrochloride g 3 Sodium hexametaphosphate g 1 Hydroxylamine hydrochloride g 1.2 Anhydrous sodium sulfite g 4 Anhydrous sodium carbonate g 50 Potassium bromide g.. 2.5 Water up to ml 1000 The developed material is rinsed with water for 30 sec. at 18 C. and fixed for 4 min. at 20 C. in a fixing bath of the following composition:

Next, the material is rinsed again for 6 min. at 18 C. and treated for 4 min. in a bleaching bath of the following composition:

Potassium dichromate g 5 Potassium bromide g 20 Potassium alum g 40 Sodium bisulfate g 0.6

Water up to ml '1000 After bleaching, the material is rinsed for 4 min. at 18 C. and fixed again in the fixing bath composed as described above. After a further rinsing for 6 min. at 18 C. the material is stabilized in the following stabilizing bath:

Anhydrous sodium carbonate g 10 Disodiu-m salt of ethylenediamine tetraacetic acid g 2 Paraformaldehyde g 5 Water up to ml 1000 A magenta wedge-image having an absorption maximum at 525 m is obtained.

Example 2 A similar silver halide emulsion as described in Example 1, wherein the color coupler is replaced by a same amount of the color coupler having the structural Formula 2 dissolved in a mixture of ml. of 0.5 N sodium hydroxide, 80 ml. of isopropanol and 80 ml. of distilled water. After the addition of the usual additives such as hardeners, wetting agents, stabilizers and the necessary amount of distilled water to obtain 1 kg. of emulsion, the latter is coated onto a cellulose triacetate support and dried. After exposure and further processing as described in Example 1, a magenta colored image is obtained having an absorption maximum of 5 30 m Example 3 To /2 kg. of a green-sensitive silver halide emulsion containing 0.0950 mol of silver chloride are added 10 g. of the color coupler having the structural Formula 4, dissolved in a mixture of 40 ml. of 1 N sodium hydroxide,

32 ml. of isopropanol and 32 ml. of distilled water. After addition of the usnal-additives such as hardeners, wetting agents, stabilizers and the necessary amount of distilled water to obtain 1 kg. of emulsion, the latter is coated to form part of a multilayer photographic color material. The multilayer photographic material consists in the in.- dicated sequence of an antihalation layer, asupport, a gelatin subbing layer, a red-sensitive silver halide emulsion layer containing .acyan-forming color coupler, a gelatin interlayer, a, layer of a green-sensitive silver halide emulsion. prepared as described above, a yellow filterlayer, a blue-sensitive silver halide emulsion layer containing a yellow-forming color coupler, and at least one gelatin overcoat as antistress layer.

The multilayer color material is exposed through a color negative and further processed as described in Example 1. A positive color image is obtained.

We claim:

1. A method of producing a magenta colored photographic image in a silver halide emulsion layer,'which comprises exposing the layer and developing the layer with an aromatic primary amine in the presence of a coupler compound having the following general formula:

in which R is an alkyl radical containing from 4 to 20 carbon atoms, and R is an aryl radical. 1

2. A method of producing a magenta colored photo graphic image in a silver halide emulsion layer, which comprises exposing the layer and developing the layer with an aromatic primary amine in the presence of a coupler compound having the following general formula:

RI I

in which R is a higher alkyl radical containing from 5 to 20 carbon atoms, and R is an aryl radical.

3. A method of producing a magenta colored photographic image in a silver halide emulsion layer, which comprises exposing the layer and developing the layer with an aromatic primary amine in the presence of a conpler compound having the following general formula:

in which R' is a lower alkyl radical, and R' is an aryl d v i s a, v

' 5. "Acolor-forming photographic developer comprising a primary aromatic amino'developing agent andaj coupler compound having the following general formula'z" I H2o 'o-'Nn o0NHa',', v in which R" is a lower alkylradical, and R' is a phenyl radical. v

6. A photographic emulsion for. preparing a photographic element for formingc-olored images comprising a water-permeable colloid as carrier for light-sensitive silver halide and a color coupler having the general formula:

Hi JiI-NHCONH in which R is an alkyl radical containing from 4 to 20 carbon atoms, and R is an aryl radical.

7. A photographic element containing at least one silver halide emulsion layer and containing in non-migratory form a coupler compound having the following general formula: v

in which R is an alkyl radical containing from 4 to 20 carbon atoms, and R is an aryl radical.

8. A photographic element containing at least one silver halide emulsion layer, which contains a coupler compound having the following general formula:

H,( J ii NHooNn -n' p in which R is an alkyll-radical containing was to 20 carbon atoms, and R is an aryl radical.

References Cited UNITED STATES PATENTS 2,369,489 2/1945 Porter et al. 96-100 3,161,512 12/1964 Greenhalgh 96-100 J. TRAVIS BROWN, Primary Examiner. 

